Template-Induced {Mn2}–Organic Framework with Lewis Acid–Base Canals as a Highly Efficient Heterogeneous Catalyst for Chemical Fixation of CO2 and Knoevenagel Condensation

The target for the self-assembly of functional microporous metal-organic frameworks (MOFs) could be realized by employing ligand-directed and/or template-induced strategies, which prompted us to explore the synthetic technique of d¹⁰ secondary-building-unit-based nanoporous frameworks. Here, the exquisite combination of a paddle-wheel [Mn₂(CO₂)₆(OH₂)₂] cluster and a TDP^6- ligand contributes one robust honeycomb framework of {(Me₂NH₂)₂[Mn₂(TDP)(H₂O)₂]·3H₂O·3DMF}_n (NUC-31; DMF = N,N-dimethylformamide), whose activated state with the removal of associated aqueous molecules characterizes the outstanding physicochemical properties of nanochannels, penta- and tetracoordinated Mn²⁺ serving as highly open metal sites, rich Lewis base sites (rows of C═O groups and N_pyridine atoms), and excellent thermal stability. Moreover, it is worth mentioning that Lewis acid-base sites on the inner surface of the channels in activated NUC-31 successfully form one unprecedented canal-shaped acid-base confined space with evenly distributed open metal sites of Mn²⁺ and N_pyridine atoms as the canal bottom as well as two rows of C═O groups serving as dyke dams. Catalytic experiments displayed that activated NUC-31 could serve as an efficient heterogeneous catalyst for the chemical fixation of CO₂ with epoxides into cyclic carbonates under mild conditions. Furthermore, NUC-31 could effectively catalyze the reaction Knoevenagel condensation, which should be ascribed to the synergistic polarization effect aroused from its plentiful Lewis base sites in the confined channel space. Hence, these results demonstrate that the employment of ligand-directed and template-dependent strategies could overcome the self-assembled barriers of functional microporous MOFs and achieve unexpected frameworks.